Nitrobenzoic acid esters of trihalogentertiary butyl alcohol



Patented Apr. 10, 1923.

UNITED STATES PATENT OFFICE.

THOMAS 'B. ALDRICH, OE DETROI IIT, MICHIGAN, ASSIGNOR TO PARKE, DAVIS & COMPANY, OF DETROIT, MICHIGAN, A CORPORATION OF MICHIGAN.

NITROBENZOIC ACID ESTERS OF TRIHALOGENTERTIARY BUTYL ALCOHOL.

Ho Drawing. Application filed April 10,

To all whom. it may concern Be it known that I, THOMAS B. ALDRICH, a citizen of the United States of America, residing at Detroit, in ,the county of Wayne and State of Michigan, have invented certain new and useful Nitrobenzoic Acid Esters of Trihalogentertiary Butyl Alcohol, of which the following is a specification.

The invention, relates to a new series of bodies which may be designated as nitro benzoic esters of tri-halogentertiary-butylalcohol. I have isolated a number of specific A QNOo 25 Place 10 grams of tri-chlorotertiary-butyl- (B) I on OH: I

Place 100 grams (or 71.4 cc.) of nitric acid (sp. g. 1.4) in a suitable flask and holding the temperature under 5060 0. add 50 grams of the finely powdered benzoic 55 ester, stirring briskly during the addition.

A' yellowish liquid results which may be alloweil to stand for a number of hours.

Add an excess of water, cooling at the same time. A yellowish oil is thrown out 00 which gradually solidifies Remove to a mortar and "grind up with excess of cold watersevral times. Collect on ,a filter and fife-crystallize repeatedly from 95% alcohol The resulting product has a melting point of OCH/\CH on. OCH/W v OCMiOH+CIiQCH=CCh-t0-LCK {CH-F116] 1922. Serial No. 551,287.

bodies belonging to this series, some of which are isomeric and others differing by the specific halogen used in the compound. As an example ofthis new series I shall describe several methods of preparation of one of the series, viz. the meta nitro benzoic ester'of tri-chlorotertiary-butyl-alcohol.

One method of preparation of meta nitro benzoic ester of tri-chlorotertiary-butylalcohol is to combine meta nitro benzoyl chloride with tri-chlorotertiary-butyl-alcohol according'to the following reaction and reheat on steam bath. Cool and decant the wash water. Continue the washing until the water is no longer acid. Allow to solid-' C. NO

about 86-88 C. and is identical in every respect with the compound obtained under method A. The yield obtained from this method is about 50%.

The formula of meta nitro benzoic acid ester of tri-chlorotertiary-butyl-alcohol may be graphically represented as follows By usin the isomeric mono nitro benzoyl chloride compounds, such as the ortho and para compounds and using method A, the corresponding ortho'and para nitro benzoic acid esters of tri-chlorotertiary-butyl-alcohol may be similarly prepared.

Three other compounds may be prepared by using tri-bromotertiary-butyl-alcohol and the three isomeric mono nitro benzoyl chlorides compounds and method A. I have prepared all of these cont-pounds which may be designated as follows Meta nitro benzoic acid tertiary-butyl-alcohol.

Ortho nitro benzoic acid ester of tribromotertiary-butyl-alcoliol.

Para nitro benzoic acid ester of tri-bromotertiary-butyl-alcohol.

The following properties are common to all of the above mentioned nitro compounds. They are crystalline and practically insoluble in water, but soluble in the organic solvents and are stable to light and ordinary atmospheric conditions.

The specific roperties of some of the compounds of t is new series are as follows:-

ester of tri-bromo- Meta. nitro benzoz'e acid ester of tri-chlorotertiary-bu-tyZ-a1e0bol.

Cal. for C H O Ncl t 32.6. Found:

Readily soluble in hot alcohol. crystallizing on cooling.

Very soluble in chloroform. acetone.ether. Insoluble in water.

Para mm benzoz'c acid esfer 0f tri-chloroterfiery-butyZ-alcohol.

tent of Very soluble in chloroform. Insoluble in water.

AgCl

Ortho nitro benzoic acid ester of tat-chloroterbiary-bwtyl-alcolwl.

Not very soluble in cold alcohol. Readily soluble, however, in hot alcohol from which it crystallizes in beautiful or stals. Melting point (uncorrected) 91 32.6. Found:

Chlorine determinations:

Sub. 0.2782; 0.2520: 0.3490: 0.3159: Agcl 0.3613: 0.3270: 0.4523.

Cal. for G l-1 0 1301 32.6: found. 32.1, 32.06, 32.29.

Meta nitro be-nzoic acid ester of t'ri-brmnoterfia-rg -batyZ-alc0h01.

Sparingly soluble in cold alcohol. May be dissolved in hot alcohol from which it crystallizes in the form of needle-like prisms. Exceedingly soluble in chloroform. soluble in ether. acetone, glacial acetic acid. Insoluble in Water.

Melting point (uncorrected) 121 C.

Bromine determinations (Carius).

Subs. 0.2807; 0.3605 AgBr, 0.3430 1 0.4420.

Calc. for C H Oj Br z 52.17. Found: 52.01. 52.14.

Pam nitro beneoz'c acid ester of tri-bromotertcry-bwtyl-alcohol.

Sparingly soluble in cold alcohol. May be dissolved in hot alcohol from which it crystallizes in the form of fine needles. Exceedingly soluble in chloroform, soluble in ether, acetone, glacial acetic acid. Insoluble in water. Melting point (uncorrected) 148 C.

Bromine determination.

Subs. 0.3001, 0.2961: AgBr, 0.3662, 0.3630.

Calc. for C,,H O NBr,:52.17. Found: 51.92: 52.18.

Ortho nitro beneoic acid esterof tri-bromo tertiarybutyZ-aleohol.

Sparingly soluble in cold alcohol. May be dissolved in hot alcohol from which it crystallizes in the form of plates similar to tho. of meta nitro benzoic acid ester of trichlorotertiary butyl alcohol. Very soluble in chloroform. ether, acetone. Soluble in glacial acetic acid. Insoluble in water. Melting points (uncorrected) 97 C.

Subs, 0.26666, 0.3107, 0.2591, 0.2415: AgBr, 0.3208. 0.3759, 0.3111, 0.2945.

Calcafor C H O NBr 52.17. Found: 51.2, 51.48. 51.1, 51.43.

Although it is generally more convenient to prepare the nitro esters b using the respective nitro benzoyl chlori es, other processes may be used, such as treating the respective nitro benzoic acids with tri-halogentertiary-butyl-alcohol andusing suitable dehydrating agents.

\Vhat I claim as my invention is 1. A new body forming one of a series which may be designated as .nltro derivatives of the benzoic acid esters of tri-halovgentertiary-butyl-a-lcohol, said body having talline form and stability under ordinary conditions.

2. A new body forming one of a series which may be designated as nitro benzoic acid esters of tri-chlorotertiary-butyl-alcohol, said body having the following characteristics; insolubility in water, solubility in or ganic solvents, crystalline form and stability under ordinary conditions. g

3. A new body forming one of a series which maybe designated as mono nitro benzoic acid esters of tri-halogentertiary-butylalcohol, said body having the following characteristics; insolnbility in Water, solubility in organic solvents, crystalline form and stability under ordinary conditions.

4. A new body forming one of a series which may be designated as mono nitro benzoic acid esters of tri-chlorotertiary-butylalcohol, said body having the following characteristics; insolubility in water, solubility in organic solvents, crystalline form and stability under ordinary conditions.

5. The new body meta nitro benzoic acid ester of tri-chlorotertiary-butyl-alcohol having the following characteristics: crystallizes from alcohol in white plates having amelting point of about 86.88 C., readily sohible in hot alcohol, crystallizing on cooling, .very

soluble in chloroform, acetone and ether, in-

soluble in water containing about 39.06% chlorine.

In testimony whereof'I afiix my signature.

THOMAS B. ALDRICH. 

